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Mechanisms of Methoxide Ion Substitution and Acid- Catalyzed Z/E Isomerization of N-Methoxyimines

Description: The second order rate constants for nucleophilic substitution by methoxide of (Z)- and (E)-O-methylbenzohydroximoyl fluorides [C6H4C(F)=NOCH3] with various substituents on the phenyl ring [p-OCH3 (1h, 2h), p-CH3 (1g, 2g), p-Cl (1f, 2f), p-H (1e, 2e), (3,5)-bis-CF3 (1i, 2i)] in 90:10 DMSO:MeOH have been measured. A Hammett plot of these rate constants vs σ values gave positive ρ values of 2.95 (Z isomer) and 3.29 (E isomer). Comparison of these rates with methoxide substitution rates for Omethylbenzohydroximoyl bromide [C6H4C(Br)=NOCH3] and Omethylbenzohydroximoyl chloride [C6H4C(Cl)=NOCH3] reveal an element effect for the Z isomers of Br:Cl:F(1e) = 2.21:1.00:79.7 and for the E isomers of Cl:F(2e) = 1.00:18.3. With the p-OCH3-imidoyl halides the following element effects are found: Br:Cl:F(1h) = 2.78:1.00:73.1 for the Z isomer and Br:Cl:F(2h) = 1.97:1.00:12.1 for the E isomer. Measurement of activation parameters revealed ∆S≠ = -17 eu for 1e and ∆S≠ = -9.9 eu for 2e. Ab initio calculations (HF/6-31+G*, MP2/6-31+G*//HF/6-31+G*, B3LYP/6- 31+G*//HF/6-31+G*, HF-SCIPCM/6-31+G*//HF/6-31+G*) were performed to define the reaction surface. These calculations demonstrate a relatively large barrier for nucleophilic attack in relation to halogen loss and support the experimental findings that this reaction proceeds by an addition-elimination mechanism (AN# + DN). The imidoyl fluorides have been used to synthesize highly functionalized O-methyloximes by reaction with enolate anions derived from malononitrile, ethyl cyanoacetate, and diethyl malonate. Acid-catalyzed isomerization of compounds containing the O-methyloxime moiety have been investigated with ab initio calculations (HF/6-31+G*, MP2/6- 31+G*//HF/6-31+G*, B3LYP/6-31+G*//HF/6-31+G*). Barriers for rotation around the C-N bond following protonation have been calculated. The calculated barriers are discussed in relation to an isomerization mechanism of protonation-rotation versus a nucleophilic catalysis.
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Date: December 2001
Creator: Dolliver, Debra D.
Partner: UNT Libraries

Isomerization Reactions in Organosilicon Chemistry

Description: Dimethylsilene, generated from the thermal gas phase reaction of 1,1-dimethyl-1-silacyclobutane, reacts with alkynes to produce silacyclobutenes or acyclic silanes. The temperature dependence of the product ratios have been determined and the relative reactivities of three different alkynes toward the 1,1-dimethylsilene has been determined. 1-Hydrido-1-methylsilene has been generated by gas phase thermal decomposition from three different precursors. Trapping studies with butadiene and trimethylsilane lead to products expected from dimethylsilylene. The most plausible explanation for these observations is that hydridomethylsilenes undergo a facile isomerization to divalent dimethylsilylene. Cycloaddition of 1,1-dimethylsilene to allene at 600°C in a flow vacuum pyrolysis system affords the first synthesis of 2-methylene-1,1-dimethylsilacyclobutane and smaller amounts of six other products. For static pyrolysis at 421°C, the 2-methylene-1,1-dimethyIsilacyclobutane isomerizes to 1,1-dimethylsilacyclopentenes. The kinetics of gas phase thermal decomposition of cyclopropyltrimethylsilane has been studied over the temperature range, 689.6-751.1 K at pressures near 14 torr. The Arrhenius parameters for formation of allyltrimethylsilane are k_1(sec^-1)=10^14.3 ± 0.1 exp(-56.5 ± 0.2 kcal mol^-1/RT) and those for the formation of E- and Z-1-propenyltrimethyIsilane are k_2(sec^-1)=10^14.9 ± 0.3 exp(-61.9 ± 0.8 kcal mol^-1/RT). The difference between activation energies has been interpreted in terms of anchimeric assistance or the β effect of the silicon atom. The syntheses of 3-trimethylsilyl-1-pyrazoline and 1-trimethyl-2-pyrazoline are described. The thermal decomposition of either pyrazoline affords four different products along with elimination of a nitrogen molecule. It was suggested that the relative rates of methylene-hydrogen migration to radical centers α and γ to silicon are approximately equal. The thermal isomerization of 3-trimethylsilyl-1-pyrazoline to 1-trimethylsilyl-2-pyrazoline has been investigated kinetically at 65°C by proton NMR spectroscopy and the reverse reaction has been detected by gas phase pyrolysis.
Date: August 1985
Creator: Kwak, Young-Woo
Partner: UNT Libraries

Graphene Layer Growth Chemistry: Five-Six-Ring Flip Reaction

Description: Reaction pathways are presented for hydrogen-mediated isomerization of a five and six member carbon ring complex on the zigzag edge of a graphene layer. A new reaction sequence that reverses orientation of the ring complex, or 'flips' it, was identified. Competition between the flip reaction and 'ring separation' was examined. Ring separation is the reverse of the five and six member ring complex formation reaction, previously reported as 'ring collision'. The elementary steps of the pathways were analyzed using density-functional theory (DFT). Rate coefficients were obtained by solution of the energy master equation and classical transition state theory utilizing the DFT energies, frequencies, and geometries. The results indicate that the flip reaction pathway dominates the separation reaction and should be competitive with other pathways important to the graphene zigzag edge growth in high temperature environments.
Date: December 1, 2007
Creator: Whitesides, R.; Domin, D.; Salomon-Ferrer, R.; Lester Jr., W.A. & Frenklach, M.
Partner: UNT Libraries Government Documents Department

Synthesis and Characterization of Dimethylbis(2-pyridyl)borate Nickel(II) Complexes: Unimolecular Square-Planar to Square-Planar Rotation around Nickel(II)

Description: This article reports the synthesis, characterization, and solution dynamics of the novel nickel(II) complexes (dimethylbis(2-pyridyl)borate)(triphenylphosphine)nickel(II) chloride (4) and (dimethylbis(2-pyridyl)borate)nickel(II) acetylacetonate (6).
Date: April 7, 2014
Creator: Celaje, Jeff A.; Pennington-Boggio, Megan K.; Flaig, Robinson W.; Richmond, Michael G. & Williams, Travis J.
Partner: UNT College of Arts and Sciences

Isomer Energy Differences for the C4H3 and C4H5 Isomers UsingDiffusion Monte Carlo

Description: A new diffusion Monte Carlo study is performed on the isomers of C{sub 4}H{sub 3} and C{sub 4}H{sub 5} emulating the methodology of a previous study [Int. J. Chem. Kinetics 33, 808 (2001)]. Using the same trial wave function form of the previous study, substantially different isomerization energies were found owing to the use of larger walker populations in the present work. The energy differences between the E and I isomers of C{sub 4}H{sub 3} were found to be 10.5 {+-} 0.5 kcal/mol and for C{sub 4}H{sub 5}, 9.7 {+-} 0.6 kcal/mol. These results are in reasonable accord with recent MRCI and CCSD(T) findings.
Date: December 1, 2007
Creator: Domin, D.; Lester Jr., W.A.; Whitesides, R. & Frenklach, M.
Partner: UNT Libraries Government Documents Department

Enantioselective Intramolecular Hydroarylation of Alkenes via Directed C-H Bond Activation

Description: Highly enantioselective catalytic intramolecular ortho-alkylation of aromatic imines containing alkenyl groups tethered at the meta position relative to the imine directing group has been achieved using [RhCl(coe){sub 2}]{sub 2} and chiral phosphoramidite ligands. Cyclization of substrates containing 1,1- and 1,2-disubstituted as well as trisubstituted alkenes were achieved with enantioselectivities >90% ee for each substrate class. Cyclization of substrates with Z-alkene isomers proceeded much more efficiently than substrates with E-alkene isomers. This further enabled the highly stereoselective intramolecular alkylation of certain substrates containing Z/E-alkene mixtures via a Rh-catalyzed alkene isomerization with preferential cyclization of the Z-isomer.
Date: May 22, 2008
Creator: Harada, Hitoshi; Thalji, Reema; Bergman, Robert & Ellman, Jonathan
Partner: UNT Libraries Government Documents Department

Femtosecond isomerization dynamics in the ethylene cation measured in an EUV-pump NIR-probe configuration

Description: Dynamics in the excited ethylene cation C{sub 2}H{sub 4}{sup +} lead to isomerization to the ethylidene configuration (HC-CH{sub 3}){sup +}, which is predicted to be a transient configuration for electronic relaxation. With an intense femtosecond EUV (extreme ultraviolet) pump pulse to populate the excited state, and an NIR (near infrared) probe pulse to produce the fragments CH{sup +} and CH{sub 3}{sup +} (which provides a direct signature of ethylidene), we measure optimum fragment yields at a probe delay of 80 fs. Also, an H{sub 2}-stretch transient configuration, yielding H{sub 2}{sup +} upon probing, is found to succeed the ethylidene configuration. We find that a simple single- or double-decay model does not match the data, and we present a modified model (introduction of an isomerization delay of 50 {+-} 25 fs) that does provide agreement.
Date: March 17, 2009
Creator: van Tilborg, Jeroen; Allison, Tom; Wright, Travis; Hertlein, Marc; Falcone, Roger; Liu, Yanwei et al.
Partner: UNT Libraries Government Documents Department

Near Degenerate Rearrangement Between the Radical Cations of Formaldehyde and Hydroxymethylene

Description: Motivated by the recent experiments of Berkowitz, a systematic theoretical study of the ion isomerization H{sub 2}CO{sup +} {yields} HCOH{sup +} has been carried out. Structures and vibrational frequencies for H{sub 2}CO{sup +}, the transition state, and the cis and trans isomers of HCOH{sup +} have been determined at the double zeta basis set self-consistent-field (SCF) level of theory. Equilibrium geometries were also predicted from SCF theory using a double zeta plus polarization (DZ+P) basis set. Final energetics were pinned down using DZ+P configuration interaction, involving a total of 16,290 configurations. The most reliable theoretical results suggest that trans-HCOH{sup +} lies 5.5 kcal above H{sub 2}CO{sup +}. Zero-point vibrational energy corrections do not change this H{sub 2}CO{sup +}-HCOH{sup +} separation. Similarly cis-HCOH{sup +} is predicted to lie 4.1 kcal above the trans isomer, and the barrier to rotation between the two HCOH{sup +} isomers is -18 kcal. The barrier to H{sub 2}CO{sup +} {yields} HCOH{sup +} rearrangement is predicted to be 49.0 kcal, or 44.4 kcal after correction for zero-point vibrational energies is made. The relationship between this cationic 1,2-hydrogen shift and the corresponding neutral rearrangement is discussed in terms of qualitative molecular orbital theory.
Date: June 1, 1980
Creator: Osamura, Y.; Goddard, J.D.; Schaefer III, H.F. & Kim, K.S.
Partner: UNT Libraries Government Documents Department

Kinetic Studies on C‐h Bond Activation in the Reaction of Triosmium Clusters with Diphosphine and Amidine Ligands

Description: The reaction of 1-(diphenylphosphino)-2-(diphenylphosphito)benzene (PP*) and Os3(CO)10(ACN) has been investigated. A combined experimental and computational study on the isomerization of 1,2-Os3(CO)10[μ-1,2-Ph2P(C6H4)P(OPh)2] (A) and 1,1-Os3(CO)10[μ-1,2-Ph2P(C6H4)P(OPh)2] (B) and reversible ortho-metalation exhibited by the triosmium cluster B are reported. The subsequent conversion of cluster B to the hydrido cluster HOs3(CO)9[μ-1,2-PhP(C6H4-η1)C6H4P(OPh)2] (E) and the benzyne-substituted cluster HOs3(CO)8(µ3-C6H4)[μ-1,2-PhP(C6H4)P(OPh)2] (N) has been established. All of these new clusters have been isolated and fully characterized in solution by IR and NMR spectroscopy; in addition, X-ray diffraction analyses have been performed on the clusters A, B, J, and N. The ortho-metalation reaction that gives cluster E is shown to be reversible, and the mechanism has been probed using selectively deuterated PP* isotopomers. Kinetic and thermodynamic isotope data, in conjunction with DFT calculations, are presented that support the existence of an intermediate unsaturated cluster in the ortho-metalation reaction. Due to interest in the coordination chemistry of formamidines, the non-symmetric amidine ligands PhNC(Me)NHPri, PhNC(Et)NHPri, and (2,4,6-Me3C6H2)NC(Me)NHPri, have been synthesized, and their reaction with Os3(CO)10(MeCN)2 has been investigated. Of the twelve new clusters prepared in section, seven have been structurally characterized by X-ray crystallography.
Date: December 2014
Creator: Yang, Li
Partner: UNT Libraries

Computational studies of the potential energy surface for O(¹D) + H₂S: Characterization of pathways involving H₂SO, HOSH, and H₂OS

Description: Article on computational studies of the potential energy surface for O(¹D) + H₂S and the characterization of pathways involving H₂SO, HOSH, and H₂OS.
Date: December 1, 1994
Creator: Goumri, Abdellatif; Rocha, John-David Ray; Laakso, Dianna; Smith, C. E. & Marshall, Paul
Partner: UNT College of Arts and Sciences

Synthesis, characterization, and kinetics of isomerization, C-H and P-C bond activation for unsaturated diphosphine-coordinated triosmium carbonyl clusters.

Description: Substitution of MeCN ligands in the activated cluster Os3(CO)10(MeCN)2 by the unsaturated diphosphine ligands (Z)-Ph2PCH=CHPPh2 (cDPPEn) or 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) proceeds rapidly at room temperature to furnish the ligand-bridged cluster 1,2-Os3(CO)10(P-P) (P-P represents cDPPEn or bpcd). Heating 1,2-Os3(CO)10(P-P) leads to the formation of the thermodynamically more stable chelating isomer 1,1-Os3(CO)10(P-P). Each compound of Os3(CO)10(P-P) has been characterized by x-ray diffraction, IR, 31P NMR and 1H NMR. Ligand isomerization kinetics have been investigated by UV-VIS and 31P NMR (for cDPPEn) or 1H NMR (for bpcd) spectroscopies. The isomerization mechanism is discussed based on the activation parameters and CO inhibition (for cDPPEn) or ligand trapping experiments (for bpcd). Thermolysis of 1,1-Os3(CO)10(bpcd) in refluxing toluene gives the hydrido cluster HOs3(CO)9[μ-(PPh2)C=C{PPh(C6H4)}C(O)CH2C(O)] and the benzyne cluster HOs3(CO)8(μ3-C6H4)[μ2,η1-PPhC=C(PPh2)C(O)CH2C(O)]. Photolysis of 1,1-Os3(CO)10(bpcd) using near UV light affords HOs3(CO)9[μ-(PPh2)C=C{PPh(C6H4)}C(O)CH2C(O)] as the sole product. HOs3(CO)8(μ3-C6H4)[μ2,η1-PPhC=C(PPh2)C(O)CH2C(O)] has been characterized in solution by IR and NMR spectroscopies. Furthermore its molecular structure has been determined by X-ray crystallography. Reversible C-H bond formation in HOs3(CO)9[μ-(PPh2)C=C{PPh(C6H4)}C(O)CH2C(O)] is demonstrated by ligand trapping studies to give 1,1-Os3(CO)9L(bpcd) (where L = CO, phosphine) via the unsaturated intermediate 1,1-Os3(CO)9(bpcd). The kinetics for reductive coupling in HOs3(CO)9[γ-(PPh2)C=C{PPh(C6H4)}C(O)CH2C(O)] and DOs3(CO)9[μ-(PPh2-d10)C=C{P(Ph-d5)(C6D4)}C(O)CH2C(O)] in the presence of PPh3 give rise to a kH/kD value of 0.88, whose magnitude supports the existence of a preequilibrium involving the hydride(deuteride) cluster and a transient arene-bound Os3 species that precedes the rate-limiting formation of 1,1-Os3(CO)9(bpcd). Strong proof for the proposed hydride(deuteride)/arene preequilibrium has been obtained from photochemical studies employing the isotopically labeled cluster 1,1-Os3(CO)10(bpcd-d4ortho), whose bpcd phenyl groups each contain one ortho hydrogen and deuterium atom. Equilibrium and kinetic isotope effects in the orthometallation step has been determined by 1H NMR in photochemical studies. Kinetics for the transformation from HOs3(CO)9[μ-(PPh2)C=C{PPh(C6H4)}C(O)CH2C(O)] to HOs3(CO)8(μ3-C6H4)[μ2,η1-PPhC=C(PPh2)C(O)CH2C(O)] has been studied by UV-VIS spectroscopy for which the mechanism is discussed.
Date: May 2008
Creator: Wu, Guanmin
Partner: UNT Libraries

The mechanism for iron-catalyzed alkene isomerization in solution

Description: Here we report nano- through microsecond time-resolved IR experiments of iron-catalyzed alkene isomerization in room-temperature solution. We have monitored the photochemistry of a model system, Fe(CO){sub 4}({eta}{sup 2}-1-hexene), in neat 1-hexene solution. UV-photolysis of the starting material leads to the dissociation of a single CO to form Fe(CO){sub 3}({eta}{sup 2}-1-hexene), in a singlet spin state. This CO loss complex shows a dramatic selectivity to form an allyl hydride, HFe(CO){sub 3}({eta}{sup 3}-C{sub 6}H{sub 11}), via an internal C-H bond-cleavage reaction in 5-25 ns. We find no evidence for the coordination of an alkene molecule from the bath to the CO loss complex, but do observe coordination to the allyl hydride, indicating that it is the key intermediate in the isomerization mechanism. Coordination of the alkene ligand to the allyl hydride leads to the formation of the bis-alkene isomers, Fe(CO){sub 3}({eta}{sup 2}-1-hexene)({eta}{sup 2}-2-hexene) and Fe(CO){sub 3}({eta}{sup 2}-1-hexene){sub 2}. Because of the thermodynamic stability of Fe(CO){sub 3}({eta}{sup 2}-1-hexene)({eta}{sup 2}-2-hexene) over Fe(CO){sub 3}({eta}{sup 2}-1-hexene){sub 2} (ca. 12 kcal/mol), nearly 100% of the alkene population will be 2-alkene. The results presented herein provide the first direct evidence for this mechanism in solution and suggest modifications to the currently accepted mechanism.
Date: May 27, 2008
Creator: Sawyer, Karma R.; Glascoe, Elizabeth A.; Cahoon, James F.; Schlegel, Jacob P. & Harris, Charles B.
Partner: UNT Libraries Government Documents Department

Pre-Steady State Kinetics of the NAD-Malic Enzyme from Ascaris suum in the Direction of Oxidative Decarboxylation of L-Malate

Description: Stopped-flow experiments in which the NAD-malic enzyme was preincubated with different reactants at near saturating substrate concentrations suggest a slow isomerization of the E:NAD:Mg complex. The lag is eliminated by preincubation with Mg˙² and malate suggesting that the formation of E:Mg:Malate either bypasses or speeds up the slow isomerization step. Circular dichroic spectral studies of the secondary structural changes of the native enzyme in the presence and absence of substrates supports the existence of conformational changes with NAD˙ and malate. Thus, a slow conformational change of the E:NAD:Mg complex is likely one of the rate-limiting steps in the pre-steady state.
Date: December 1991
Creator: Rajapaksa, Ranjani, 1949-
Partner: UNT Libraries

Quantum effects in unimolecular reaction dynamics

Description: This work is primarily concerned with the development of models for the quantum dynamics of unimolecular isomerization and photodissociation reactions. We apply the rigorous quantum methodology of a Discrete Variable Representation (DVR) with Absorbing Boundary Conditions (ABC) to these models in an attempt to explain some very surprising results from a series of experiments on vibrationally excited ketene. Within the framework of these models, we are able to identify the experimental signatures of tunneling and dynamical resonances in the energy dependence of the rate of ketene isomerization. Additionally, we investigate the step-like features in the energy dependence of the rate of dissociation of triplet ketene to form {sup 3}B{sub 1} CH{sub 2} + {sup 1}{sigma}{sup +} CO that have been observed experimentally. These calculations provide a link between ab initio calculations of the potential energy surfaces and the experimentally observed dynamics on these surfaces. Additionally, we develop an approximate model for the partitioning of energy in the products of photodissociation reactions of large molecules with appreciable barriers to recombination. In simple bond cleavage reactions like CH{sub 3}COCl {yields} CH{sub 3}CO + Cl, the model does considerably better than other impulsive and statistical models in predicting the energy distribution in the products. We also investigate ways of correcting classical mechanics to include the important quantum mechanical aspects of zero-point energy. The method we investigate is found to introduce a number of undesirable dynamical artifacts including a reduction in the above-threshold rates for simple reactions, and a strong mixing of the chaotic and regular energy domains for some model problems. We conclude by discussing some of the directions for future research in the field of theoretical chemical dynamics.
Date: December 1, 1995
Creator: Gezelter, J.D.
Partner: UNT Libraries Government Documents Department

Nano-scale materials

Description: This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). Highly selective, alumina-supported molybdenum carbonitrides were prepared by solution impregnation using the metal amide Mo{sub 2}(N(CH{sub 3}){sub 2}){sub 6} as a molecular precursor. On the basis of relative weight percents, these materials demonstrate a 5- to 8-fold increase in catalytic activity over similar materials prepared by traditional solid-state approaches. The catalytic activities of these materials are very dependent upon the type of alumina support used. Impregnation of Mo{sub m}C{sub x}N{sub y} into preformed alumina pellets resulted in a material that specifically isomerized n-heptane into equal amounts of 2- and 3-methylhexanes, as well as iso-butane. No evidence of aromatic products was observed at operating temperatures below 420{degrees}C. The product selectivity of the isomers was 56% at a n-heptane conversion efficiency of 57%. Impregnating Mo{sub m}C{sub x}N{sub y} into an alumina powder resulted in an extremely selective aromatized and dehydrogenated material. The products from this material consist only of aromatics and n-heptenes with less than 2% isomerization or cracking products.
Date: December 31, 1998
Creator: Barrera, J.; Smith, D.C. & Devlin, D.J.
Partner: UNT Libraries Government Documents Department

Atom transfer and rearrangement reactions catalyzed by methyltrioxorhenium, MTO

Description: Methyltrioxorhenium (MTO) catalyzes the desulfurization of thiiranes by triphenylphosphine. Enormous enhancement in rate is observed when the catalyst is pretreated with hydrogen sulfide prior to the reaction. Using 2-mercaptomethylthiophenol as a ligand, the author synthesized several model complexes to study the mechanism of this reaction. With suitable model systems, they were able to show that the active catalyst is a Re(V) species. The reactions are highly stereospecific and very tolerant to functional groups. As part of the studies, he synthesized and crystallographically characterized the first examples of neutral terminal and bridging Re(V)sulfidocomplexes. Some of these complexes undergo fast oxygen atom transfer reactions with organic and inorganic oxidants. Studies on these model complexes led them to the discovery that MTO catalyzes the selective oxidation of thiols to disulfides. This report contains the Introduction; ``Chapter 6: Isomerization of Propargylic Alcohols to Enones and Enals Catalyzed by Methylrhenium Trioxide``; and Conclusions.
Date: May 10, 1999
Creator: Jacob, J.
Partner: UNT Libraries Government Documents Department

Microwave processing improvements for methane conversion to ethylene

Description: This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The project`s objective was to investigate microwave enhanced catalysis. Published work by others had demonstrated improved selectivity in microwave-driven catalytic conversion of 2-methylpentane to its isomers. We reproduced their experiment, discovering that there is no improvement in selectivity using microwaves. The selectivity at a given conversion was the same for both microwave heated and conventionally heated catalyst beds. Meetings with the authors of the previously published work led to the conjecture that their catalyst was not being prepared properly, leading to anomalously low selectivity for their conventional heating runs. An optical temperature diagnostic suitable for use on a microwave applicator was developed and characterized in this project. This pyrometer can measure the temperature of small scale features on the catalyst bed, and it has a fast response that can follow the rapid heating often encountered in a microwave processing system. The behavior of the microwave applicator system was studied, and theoretical models were developed to yield insight about the stability and control of the system.
Date: August 1, 1997
Creator: Stringfield, R.; Ott, K.; Nelson, E.; Anderson, G.; Chen, Dye-Zone; Dyer, T. et al.
Partner: UNT Libraries Government Documents Department

Synthesis and characterization of nanophase zirconia : reverse micelle method and neutron scattering study.

Description: Zirconia is an important transition-metal oxide for catalytic applications. It has been widely used in automotive exhaust treatment, methanol synthesis, isomerization, alkylation, etc. [1]. Nanophase materials have unique physiochemical properties such as quantum size effects, high surface area, uniform morphology, narrow size distribution, and improvement of sintering rates[2]. Microemulsion method provides the means for controlling the microenvironment under which specific chemical reactions may occur in favoring the formation of homogeneous, nanometer-size particles. In this paper, we report the synthesis of nanophase zirconia and the characterization of the microemulsions as well as the powders by small- and wide-angle neutron scattering techniques.
Date: November 23, 1998
Creator: Li, X.
Partner: UNT Libraries Government Documents Department

Synthesis and characterization of quinoxaline-functionalized, cage-annulated oxa- and thiacrown ethers and reaction chemistry of the diphosphine ligand 2,3-bis(diphenylphosphino)-N-p-tolylmaleimide (bmi) at triosmium carbonyl clusters.

Description: Quinoxaline-functionalized, cage-annulated oxa- and thiacrown ethers have been synthesized as possible specific metal host systems. The synthesis and characterization of quinoxaline-functionalized, cage-annulated oxa- and thiacrown ethers have been described. The characterization of these host systems have been fully achieved in solution by using various techniques such as IR, 1H NMR, and 13C NMR spectroscopic methods, high-resolution mass spectrometry (HRMS), elemental microanalysis, and X-ray crystallographic analysis in case of one quinoxaline-functionalized, cage-annulated oxacrown ether compound. The synthesis of the diphosphine ligand 2,3-bis(diphenylphosphino)-N-p-tolylmaleimide (bmi) is described. The substitution of the MeCN ligands in the activated cluster 1,2-Os3(CO)10(MeCN)2 by the diphosphine ligand bmi proceeds rapidly at room temperature to furnish a mixture of bridging and chelating Os3(CO)10(bmi) isomers and the ortho-metalated product HOs3(CO)9[μ-(PPh2)C=C{PPh(C6H4)}C(O)N(tolyl-p)C(O)]. Thermolysis of the bridging isomer 1,2-Os3(CO)10(bmi) under mild conditions gives the chelating isomer 1,1-Os3(CO)10(bmi), whose molecular structure has been determined by X-ray crystallography. The kinetics for the ligand isomerization have been investigated by UV-vis and 1H NMR spectroscopy in toluene solution over the temperature range of 318-348 K. On the basis of kinetic data conducted in the presence of added CO and the Eyring activation parameters, a non-dissociative phosphine migration across one of the Os-Os bonds is proposed. Orthometalation of one of the phenyl groups associated with the bmi ligand is triggered by near-UV photolysis of the chelating cluster 1,1- Os3(CO)10(bmi).
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Date: December 2006
Creator: Poola, Bhaskar
Partner: UNT Libraries

Intermediate-Valence Tautomerism in Decamethylytterbocene Complexes of Methyl-Substituted Bipyridines

Description: Multiconfigurational, intermediate valent ground states are established in several methyl-substituted bipyridine complexes of bispentamethylcyclopentadienylytterbium, Cp*{sub 2} Yb(Me{sub x}-bipy). In contrast to Cp*{sub 2} Yb(bipy) and other substituted-bipy complexes, the nature of both the ground state and the first excited state are altered by changing the position of the methyl or dimethyl substitutions on the bipyridine rings. In particular, certain substitutions result in multiconfigurational, intermediate valent open-shell singlet states in both the ground state and the first excited state. These conclusions are reached after consideration of single-crystal x-ray diffraction (XRD), the temperature dependence of x-ray absorption near-edge structure (XANES), extended x-ray absorption fine-structure (EXAFS), and magnetic susceptibility data, and are supported by CASSCF-MP2 calculations. These results place the various Cp*{sub 2}Yb(bipy) complexes in a new tautomeric class, that is, intermediate-valence tautomers.
Date: January 25, 2011
Creator: Booth, Corwin H.; Kazhdan, Daniel; Werkema, Evan L.; Walter, Marc D.; Lukens, Wayne W.; Bauer, Eric D. et al.
Partner: UNT Libraries Government Documents Department

Modeling and Experimental Investigation of Methylcyclohexane Ignition in a Rapid Compression Machine

Description: A new mechanism for the oxidation of methylcyclohexane has been developed. The mechanism combined a newly-developed low temperature mechanism with a previously developed high temperature mechanism. Predictions from the chemical kinetic model have been compared to experimentally measured ignition delay times from a rapid compression machine. Predicted ignition delay times using the initial estimates of the methylcyclohexyl peroxy radical isomerization rate constants were much longer than those measured at low temperatures. The initial estimates of isomerization rate constants were modified based on the experimental findings of Gulati and Walker that indicate a much slower rate of isomerization. Predictions using the modified rate constants for isomerizations yielded faster ignition at lower temperatures that greatly improved the agreement between model predictions and the experimental data. These findings point to much slower isomerization rates for methylcyclohexyl peroxy radicals than previously expected.
Date: October 13, 2005
Creator: Pitz, W J; Naik, C V; Mhaold?in, T N; Curran, H J; Orme, J P; Simmie, J M et al.
Partner: UNT Libraries Government Documents Department